Structural Effects

electron delocalization (Resonance)

CH2 .. CH Cl : ..
.. O C .. .. NH2 .. NH2

.. Cl : ..

:O: CH3 C .. O H ..

 electron delocalization (Resonance)

Structural Effects

 electron delocalization (Resonance)

Structural Effects

 electron delocalization (Resonance)

Structural Effects
:O: C H

:O:

.. :O

.. :O: N+

.. NH2

Hyperconjugation

Structural Effects
H H C CH CH2 H

H C CH CH2 H

..-

..+ H C CH CH2 H

..H C CH CH2 H
+

Hyperconjugation

Structural Effects

Dienes

CH2

CH CH CH2

cumulative

conjugated

isolated

Hyperconjugation
H H C H

Structural Effects
H H C H
+

H H C H
+

..

..
-

Hyperconjugation
H H C C H

Structural Effects
O H
H O H C C H H +

Structural Effects
+

CH3

CH3

CH2

CH2 H3C

CH3 C
+

CH3

H
-

:CH3

O2N

C: H H

. CH

C. H

Inductive Effect

Structural Effects

Electron attracting inductive with excess positive charges effect

R N R R those with electronegative atoms NH2 OH OCH3 F
+ +

NH3

NO2

Cl Br groups exhibiting orbital electronegativity C N N N

those with easily polarizable valence electrons I

-

Inductive Effect

Structural Effects

Electron attracting inductive effect +

H3C Cl
+ CH3 ++ CH2 Cl
CH3 H3C N CH3
-+

CH3

+ CH2

O H +

Inductive Effect

Structural Effects

Electron repelling inductive alkyl groups effect

CH3 negative groups COO
-

O H3C C O
--

H3C

H3C CH C N H3C

O R C O C

O O O R

O S O O

Steric Effect

Structural Effects

Hydrogen Bonding
F O N H + H + H +

Structural Effects
F O N H H H + + +

H O H R O H O H H H O R

H
OH OH

O H O R C O H O C R

H C O O H

Acids and Bases

BrnstedLowry Acids and Bases

An acid is a proton donor A base is a proton acceptor
HBr acid + H2O base NH4 + OH Br + H3O

NH3 + H2O base acid

Note that water can act as an acid or a base

Acids and Bases

BrnstedLowry Acids and Bases

HBr HBr acid + + H2O H O H Br + H3O Br + O H H conjugate acid H

base

conjugate base

Every acidbase reaction involving proton transfer has two conjugate acidbase pairs.

Acids and Bases

Lewis Acids and Bases

A Lewis acid is an electron pair acceptor.

(think empty orbital)

A Lewis base is an electron pair donor.

(think filled orbital) The result of a Lewis acidbase reaction is often called an adduct.

Acids and Bases

Lewis Acids and Bases

O H H H

Lewis acid Electron deficient

Lewis base Electron rich

Adduct New covalent bond

Acids and Bases

Lewis Acids and Bases

Examples of Lewis Acids: Fe3+ AlCl3 H3O+ Examples of Lewis Bases:
NH3 H2O Cl

Acids and Bases

Acids and Bases

pH = log[H3O+]

HA + H2O A

A + H3O H3O HA

Ka =

pKa = log (Ka)

Acids and Bases

Acid Strength
HA + H2O H3O+ + A-

A
E N E R G Y

WEAK ACID -Has a strong conj. base ( higher energy) STRONG ACID -Has a weak conj. base ( lower energy)

HA

ionization easier

Acids and Bases

Acid Strength

Acids and Bases

Factors that influence stability of the conjugate base include: Resonance Electronegativity Atomic Size Hybridization Inductive Effects

Resonance Effects
increasing quality of resonance

Acids and Bases

pKa Values 18 R CH3 CH3 45 30 NH2 25 25 20 O R C NH2 15 R NH2 28

R OH

OH 10 O R C OH 5

O CH3O C CH3 O R C CH3 O O

R C CH2 C R 9

The Acetate Ion

O CH3 C OH -H+
Base

Acids and Bases

O CH3 C O

acetic acid

O CH3 C O

acetate ion Resonance Stabilized Equivalent structures (charges on oxygens)

The Phenolate Ion

O O O

Acids and Bases

O O

More resonance structures, but not more stable than acetate Nonequivalent structures (note charges on carbon and oxygen)

Acids and Bases

Electronegativity
increasing electronegativity

pKa Values 34 16 RCH 3 RNH 2 ROH 45 35 18

CH4 NH3 H2O HF

>45

O R C CH3 20 O R C NH2 O R C OH 15

3.5

Electronegativity
increasing size

Acids and Bases

HF HCl HBr HI

3.5 7 9 10

pKa Values F 1.36 H2O Cl Br I 1.81 1.95 2.16 H2S H2Se H2Te

16 7 4 3

O R C OH O R C SH S R C SH

Inductive Effects
Electron-withdrawing Groups

Acids and Bases

Electron-donating Groups

Cl

+ C

+ CH3

F, Cl, Br, O, N

R, CH3, B, Si

electronegative elements alkyl groups and elements less electronegative than carbon pull electron density push electron density toward carbon away from carbon

Acids and Bases

Inductive Effects
Chlorine helps to stabilize CO2 by withdrawing electrons

Cl

+O C O

This effect diminishes with distanceit extends for about 3 bonds

+ + + Cl C C C

Acids and Bases

increasing electronegativity

Inductive Effects
pKa Values 3.13 CH3 Cl COOH

increasing substitution

I Br Cl F

CH2COOH

4.75

CH2COOH 2.87 CH2COOH 2.81 CH2COOH 2.66

CH2 Cl

COOH 2.81 1.29

Cl Cl

CH Cl C Cl

COOH COOH

0.65

e- pair acceptor electron poor may possess formal positive charge incomplete octets greatly reduced e- density those that can yield e- poor species

Electrophiles
R R C+ R
: CH2

R.

X.
NO2+
R C+ O

X2 in protic solvent
O R C O OH

AlCl3

CO2 H2O

SO3 SO3H
+

+ CH3

AlCl4

H+

BF3 FeBr3

Nucleophiles
q

e- pair donor excess negative charges fractional negative charges may have a lone pair e-

OHRONH2-

CN-

R R C: R

O R C O-

X-

N3O-